Crystal structure of 2-[(2E)-2-methyl-3-phenyl­prop-2-en-1-yl­idene]-N-phenyl­hydrazinecarboxamide

Saritha, S.R.; Anitha, L.; Layana, S.R.; Sithambaresan, M.; Sudarsanakumar, M.R.

doi:10.1107/S2056989018018376

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ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 163-166

https://doi.org/10.1107/S2056989018018376

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Crystal structure of 2-[(2E)-2-methyl-3-phenylprop-2-en-1-ylidene]-N-phenylhydrazinecarboxamide

S. R. Saritha,^a L. Anitha,^a S. R. Layana,^a M. Sithambaresan ^b ^* and M. R. Sudarsanakumar ^a

^aDepartment of Chemistry, Mahatma Gandhi College, University of Kerala, Thiruvananthapuram 695 004, Kerala, India, and ^bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka
^*Correspondence e-mail: msithambaresan@gmail.com

Edited by J. Jasinsk, Keene State College, USA (Received 3 December 2018; accepted 28 December 2018; online 8 January 2019)

The title compound, C₁₇H₁₇N₃O, crystallizes with two independent molecules in the asymmetric unit. The semicarbazone moieties of these independent molecules (I and II) are essentially planar [maximum deviation of 0.042 (1) Å in molecule I and 0.041 (1) Å in molecule II], with the terminal phenyl rings twisted away from the mean plane of the semicarbazone moiety, making dihedral angles of 60.26 (8) and 28.76 (9)° in molecule I and 31.07 (9) and 35.45 (8)° in molecule II. The molecules both exhibit an E configuration with respect to the C=C and azomethine C=N bonds. In the crystal, two classical N—H⋯O hydrogen-bonding interactions are present between the two molecules, forming a centrosymmetric dimer, while a weak C—H⋯O non-classical hydrogen-bonding interaction, with a donor–acceptor distance of 3.476 (2) Å, interconnects two neighbouring centrosymmetric dimers to form a cage-like structure. These cage structures are interconnected by weak C—H⋯π interactions with an H⋯π distance of 2.790 Å, forming supramolecular chains along the c-axis direction.

Keywords: crystal structure; semicarbazone; phenylhydrazinecarboxamide.

CCDC reference: 1887613

1. Chemical context

Semicarbazones are oxygen and nitrogen contributor ligands whose significance lies in their versatility of molecular sequence, which allows diverse geometries to be obtained. Semicarbazones exhibit amido–iminol tautomerism in solution due to the interaction of solvent molecules, but generally exist in the amido form in the solid state. The FT–IR and NMR spectra of semicarbazones indicate the existence of a keto form in the solid state that can be confirmed by single crystal X-ray diffraction analysis (Kurup et al., 2011 ; Sreekanth et al., 2004 ). Biological properties linked to antimicrobial (Siji et al., 2010 ) and antiparasitic (Soares et al., 2011 ) effects make semicarbazones important ligands in coordination chemistry. Compared to Gentamycin, a commonly used antibiotic, N⁴-phenylsemicarbazone derivatives exhibit moderate antibacterial activity at higher concentrations and also show DNA cleavage properties (Layana et al., 2016 ). Semicarbazones can function as brilliant ligands in a variety of metal ions (Kala et al., 2007 ) and co-ordinate to metal ions either in neutral (Siji et al., 2011 ) or in anionic forms (Reena et al., 2008 ). Structural studies of many semicarbazones and N⁴-phenylsemicarbazones have been reported and some of them adopt an E configuration with respect to the azomethine double bond along with both inter- and intramolecular hydrogen-bonding interactions (Reena et al., 2010 ; Layana et al., 2014 , 2018 ). Semicarbazones form complexes with a variety of structural features such as monomer, dimer and one-dimensional polymers (Kunnath et al., 2016 ). α-Methyl-trans-cinnamaldehyde, a precursor for the synthesis of α-methyl-trans-cinnamaldehyde-N⁴-phenylsemicarbazone, has significant antifungal activity and can self-couple and form complexes with some transition metals (Shreaz et al., 2011 ). The diverse structural features and substantial biological applications have prompted us to synthesize a new semicarbazone derived from α-methyl-trans-cinnamaldehyde and N⁴-phenylsemicarbazide.

2. Structural commentary

The title compound crystallizes in the triclinic space group P $[\overline{1}]$ symmetry with two independent molecules, I and II, in the asymmetric unit (Fig. 1). The semicarbazone units in I and II are essentially planar, with maximum deviations from the least-squares plane of 0.042 (1) Å for N2 in molecule I and 0.041 (1) Å for N4 in molecule II. The terminal phenyl rings in both two molecules are twisted away from the semicarbazone mean plane, making dihedral angles of 60.26 (8) and 28.76 (9)° in molecule I and 31.07 (9) and 35.45 (8)° in molecule II. Both molecules exist in an E configuration with respect to the C=C and azomethine C=N bonds. The azomethine C=N and keto C=O bond lengths [1.273 (2) and 1.2269 (17) Å, respectively] in molecule I are shorter than those for molecule II [1.2766 (19) Å and 1.2302 (18) Å respectively]. In contrast, the C=N and C=O bond lengths bond lengths reported for the two independent molecules of 2-benzoylpyridine semicarbazone are 1.294 (2) and 1.295 (2) Å and 1.2360 (19) and 1.2390 (19) Å respectively (de Lima et al., 2008 ).

Figure 1
ORTEP diagram showing the two molecules in the asymmetric unit, with atom labels and 50% probability displacement ellipsoids.

3. Supramolecular features

In the crystal, two classical and one non-classical hydrogen-bonding interactions are observed. Molecules I and II are linked into centrosymmetric dimers through N2—H2′⋯O2 and N5—H5′⋯O1 hydrogen bonds with D⋯A distances of 2.808 (2) Å, and 2.8639 (19) Å, respectively (Fig. 2, Table 1), while C13—H13⋯O2 interactions with a D⋯A distance of 3.476 (2) Å, interconnect adjacent dimers, creating cage-like structures that are linked by weak C—H⋯π interactions into supramolecular chains along the c-axis direction (Fig. 3). No significant π–π interactions occur. The packing viewed along the b axis is shown in Fig. 4.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5′⋯O1	0.88 (1)	1.99 (1)	2.8639 (19)	174 (2)
N2—H2′⋯O2	0.88 (1)	1.93 (1)	2.808 (2)	176 (2)
N3—H3′⋯N1	0.87 (1)	2.13 (2)	2.6146 (18)	115 (1)
N6—H6′⋯N4	0.87 (1)	2.17 (2)	2.6261 (19)	112 (2)
C13—H13⋯O2ⁱ	0.93	2.64	3.476 (2)	149
C32—H32⋯Cg1ⁱⁱ	0.93	2.79	3.518 (2)	136
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y, -z+2.

Figure 2
N—H⋯O hydrogen bonds and weak C—H⋯O intermolecular interactions (dashed lines) generating centrosymmetric dimers and a cage-like structure.

Figure 3
Weak C—H⋯π intermolecular interactions (solid cones), linking the dimeric cage-like structures into a chain along the c axis.

Figure 4
The packing viewed along the b axis.

3.1. Database survey

The structure of the title compound has not previously been reported (CSD version 5.39, update of August 2018; Groom et al., 2016 ). All geometric parameters in the title compound agree well with those reported in the literature with the C10—N1/C27—N4 [1.273 (2) and 1.2766 (19) Å], N1— N2/N4—N5 [1.3691 (17) and 1.3679 (18) Å] and C11—O1/C28—O2 [1.2269 (17) and 1.2302 (18) Å] bond distances being comparable to those in benzaldehyde-N⁴-phenylsemicarbazone [1.273 (2), 1.369 (2) and 1.225 (2) Å; Layana et al., 2014] and vanillin-N-phenylthiosemicarbazone [1.2726 (17), 1.3801 (15) and 1.2404 (15) Å; Layana et al., 2016]

4. Synthesis and crystallization

Hot ethanolic solutions of N⁴-phenylsemicarbazide (0.1512 g, 1 mmol) and α-methyl-trans-cinnamaldehyde (0.14 ml, 1 mmol) were mixed and refluxed for about 4 h. Colourless block-shaped crystals of the title compound (yield 83%) were separated by filtration, washed with ethanol and dried over P₄O₁₀ in vacuo. Single crystals (m.p. 463±2 K) were obtained by slow evaporation of a 1:1 mixture of ethyl acetate and ethanol.

Analysis calculated: C, 73.03; H, 6.09, N, 15.04%. Found: C, 72.66; H, 6.32; N, 15.29%. Spectrometric data. FT–IR ν_max (KBr, cm⁻¹): The spectrum of the title compound shows characteristic absorption bands of the main functional groups at IR (ν_max, cm⁻¹): 3379 (⁴NH), 3192 (²NH), 1685 (C=O) 3072, 2960 (C—H aromatic), 1591 (C=N), 1029 (N—N). FT–Raman (cm⁻¹) 3055 (N—H), 1613 (C=O), 1577 (C=N), 1137 (N—N). ¹H NMR (400 MHz) (DMSO-d₆, ppm): δ_H 2.2 (s, 3H, methyl), 7–7.5 (m, 10H, Ar—H), 6.7 (s, 1H, methine), 7.7 (s, 1H, azomethine), 8.6 (s, 2H, amine), 10.6 (s, 1H, iminol H). ¹³C NMR (400 MHz) (DMSO-d₆, ppm): δ_C 135.2 (C6), 129.12 (C1 and C5), 128.4 (C2 and C4), 119.6 ppm (C3), 152.9 (C7), 146.4 (C8), 138.9 (C9), 136.5 (C10), 12.9 (C17), 134.3 (C11), 128.5 ppm (C12 and C16), 127.4 ppm (C13 and C15) and 122.4 ppm (C14). UV–visible (200–1000, nm): 268 (π–π*), 342 (n–π*).

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Reflections ( $[\overline{1}]$ $[\overline{1}]$ 1) and (001) were omitted due to bad agreement. All hydrogen atoms bound to carbon atoms were positioned geometrically with C—H distances of 0.93–0.96 Å and refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl). The NH hydrogen atoms were located in a difference-Fourier map and refined with N—H restrained to 0.88±0.01 Å.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₇N₃O
M_r	279.33
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	10.2140 (6), 10.5133 (8), 15.3297 (10)
α, β, γ (°)	106.652 (3), 99.111 (3), 97.416 (4)
V (Å³)	1530.51 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.60 × 0.50 × 0.50

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.939, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	12172, 7346, 4038
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.175, 0.95
No. of reflections	7346
No. of parameters	397
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.23
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXL2014 (Sheldrick, 2015 ), SHELXS97 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1887613

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018018376/jj2206sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018018376/jj2206Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018018376/jj2206Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXL2014 (Sheldrick, 2015); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

2-[(2E)-2-Methyl-3-phenylprop-2-en-1-ylidene]-N-phenylhydrazinecarboxamide top

Crystal data top

C₁₇H₁₇N₃O	Z = 4
M_r = 279.33	F(000) = 592
Triclinic, P1	D_x = 1.212 Mg m⁻³
a = 10.2140 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.5133 (8) Å	Cell parameters from 3309 reflections
c = 15.3297 (10) Å	θ = 2.6–27.7°
α = 106.652 (3)°	µ = 0.08 mm⁻¹
β = 99.111 (3)°	T = 296 K
γ = 97.416 (4)°	Block, colorless
V = 1530.51 (18) Å³	0.60 × 0.50 × 0.50 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	7346 independent reflections
Radiation source: fine-focus sealed tube	4038 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω and φ scan	θ_max = 28.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→12
T_min = 0.939, T_max = 0.948	k = −13→13
12172 measured reflections	l = −20→15

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.175	w = 1/[σ²(F_o²) + (0.1017P)²] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max < 0.001
7346 reflections	Δρ_max = 0.16 e Å⁻³
397 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.88173 (19)	−0.1561 (2)	0.82683 (13)	0.0630 (5)
H1	0.8824	−0.0637	0.8438	0.076*
C2	0.9866 (2)	−0.2034 (3)	0.86846 (15)	0.0723 (6)
H2	1.0576	−0.1430	0.9125	0.087*
C3	0.9863 (2)	−0.3387 (3)	0.84506 (16)	0.0753 (6)
H3	1.0568	−0.3706	0.8732	0.090*
C4	0.8822 (2)	−0.4271 (2)	0.78030 (15)	0.0734 (6)
H4	0.8818	−0.5194	0.7647	0.088*
C5	0.7773 (2)	−0.3802 (2)	0.73766 (13)	0.0613 (5)
H5	0.7073	−0.4415	0.6933	0.074*
C6	0.77527 (16)	−0.2438 (2)	0.76005 (12)	0.0497 (4)
C7	0.66419 (17)	−0.18955 (19)	0.71894 (12)	0.0502 (4)
H7	0.6304	−0.1251	0.7604	0.060*
C8	0.60596 (15)	−0.22156 (18)	0.62933 (11)	0.0442 (4)
C9	0.64815 (19)	−0.3180 (2)	0.55182 (13)	0.0611 (5)
H9A	0.7350	−0.3360	0.5739	0.092*
H9B	0.6534	−0.2795	0.5025	0.092*
H9C	0.5834	−0.4008	0.5290	0.092*
C10	0.49813 (15)	−0.15284 (18)	0.60452 (11)	0.0448 (4)
H10	0.4637	−0.0979	0.6512	0.054*
C11	0.29530 (15)	−0.10122 (17)	0.41634 (11)	0.0438 (4)
C12	0.32548 (15)	−0.18810 (17)	0.25412 (11)	0.0447 (4)
C13	0.42849 (18)	−0.2055 (2)	0.20670 (13)	0.0649 (6)
H13	0.5143	−0.2049	0.2382	0.078*
C14	0.4051 (2)	−0.2239 (3)	0.11315 (14)	0.0850 (8)
H14	0.4754	−0.2355	0.0815	0.102*
C15	0.2788 (2)	−0.2254 (3)	0.06550 (14)	0.0777 (7)
H15	0.2634	−0.2373	0.0020	0.093*
C16	0.17664 (19)	−0.2093 (2)	0.11236 (13)	0.0640 (5)
H16	0.0907	−0.2110	0.0804	0.077*
C17	0.19852 (16)	−0.1905 (2)	0.20641 (12)	0.0541 (5)
H17	0.1278	−0.1794	0.2377	0.065*
C18	−0.33204 (19)	0.2586 (2)	0.20723 (13)	0.0665 (6)
H18	−0.3167	0.1721	0.1801	0.080*
C19	−0.4276 (2)	0.3093 (3)	0.15904 (15)	0.0787 (7)
H19	−0.4753	0.2573	0.0999	0.094*
C20	−0.4518 (2)	0.4367 (3)	0.19863 (16)	0.0793 (7)
H20	−0.5171	0.4706	0.1670	0.095*
C21	−0.3796 (2)	0.5128 (3)	0.28446 (17)	0.0769 (6)
H21	−0.3953	0.5993	0.3110	0.092*
C22	−0.2836 (2)	0.4633 (2)	0.33250 (14)	0.0643 (5)
H22	−0.2347	0.5174	0.3908	0.077*
C23	−0.25859 (16)	0.3344 (2)	0.29541 (12)	0.0507 (4)
C24	−0.15906 (16)	0.27357 (19)	0.34168 (12)	0.0498 (4)
H24	−0.1223	0.2101	0.3017	0.060*
C25	−0.11244 (15)	0.29476 (17)	0.43239 (11)	0.0431 (4)
C26	−0.15538 (17)	0.38927 (19)	0.51113 (12)	0.0516 (4)
H26A	−0.0976	0.4761	0.5297	0.077*
H26B	−0.1493	0.3543	0.5627	0.077*
H26C	−0.2469	0.3982	0.4916	0.077*
C27	−0.01521 (15)	0.21447 (17)	0.45568 (11)	0.0451 (4)
H27	0.0122	0.1537	0.4079	0.054*
C28	0.17376 (15)	0.13993 (19)	0.63940 (12)	0.0474 (4)
C29	0.17182 (15)	0.24127 (19)	0.80442 (12)	0.0482 (4)
C30	0.1829 (2)	0.3675 (2)	0.86669 (14)	0.0740 (6)
H30	0.1683	0.4397	0.8452	0.089*
C31	0.2159 (2)	0.3874 (3)	0.96110 (15)	0.0878 (7)
H31	0.2219	0.4729	1.0029	0.105*
C32	0.23933 (19)	0.2836 (3)	0.99329 (15)	0.0733 (6)
H32	0.2616	0.2974	1.0569	0.088*
C33	0.2302 (2)	0.1594 (3)	0.93208 (15)	0.0766 (7)
H33	0.2476	0.0882	0.9540	0.092*
C34	0.1954 (2)	0.1371 (2)	0.83737 (14)	0.0675 (5)
H34	0.1880	0.0510	0.7961	0.081*
N1	0.44999 (12)	−0.16681 (14)	0.51975 (9)	0.0447 (3)
N2	0.34882 (14)	−0.09748 (16)	0.50394 (10)	0.0485 (4)
N3	0.35427 (14)	−0.17255 (17)	0.34979 (10)	0.0536 (4)
N4	0.03382 (12)	0.22481 (14)	0.53988 (9)	0.0455 (3)
N5	0.12237 (14)	0.14139 (16)	0.55249 (10)	0.0516 (4)
N6	0.13105 (14)	0.22397 (17)	0.70885 (10)	0.0538 (4)
O1	0.20160 (11)	−0.04300 (13)	0.40141 (8)	0.0525 (3)
O2	0.25451 (13)	0.06620 (15)	0.65140 (8)	0.0648 (4)
H3'	0.4260 (12)	−0.1964 (17)	0.3742 (11)	0.049 (5)*
H5'	0.1507 (17)	0.0898 (17)	0.5059 (9)	0.060 (6)*
H6'	0.080 (2)	0.276 (2)	0.6905 (15)	0.087 (7)*
H2'	0.3176 (16)	−0.0501 (17)	0.5509 (9)	0.055 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0670 (11)	0.0636 (14)	0.0591 (11)	0.0160 (10)	0.0032 (9)	0.0238 (10)
C2	0.0595 (11)	0.0850 (18)	0.0701 (13)	0.0139 (11)	−0.0047 (10)	0.0299 (13)
C3	0.0660 (12)	0.0986 (19)	0.0719 (14)	0.0403 (12)	0.0071 (11)	0.0358 (14)
C4	0.0886 (14)	0.0696 (15)	0.0705 (14)	0.0405 (12)	0.0118 (12)	0.0262 (12)
C5	0.0664 (11)	0.0615 (14)	0.0568 (11)	0.0221 (9)	0.0036 (9)	0.0204 (10)
C6	0.0519 (9)	0.0611 (12)	0.0446 (10)	0.0185 (8)	0.0118 (8)	0.0253 (9)
C7	0.0561 (10)	0.0558 (12)	0.0463 (10)	0.0227 (8)	0.0123 (8)	0.0209 (9)
C8	0.0415 (8)	0.0493 (10)	0.0467 (10)	0.0124 (7)	0.0108 (7)	0.0198 (8)
C9	0.0615 (11)	0.0734 (14)	0.0521 (11)	0.0290 (10)	0.0109 (8)	0.0186 (10)
C10	0.0455 (8)	0.0494 (11)	0.0446 (9)	0.0136 (7)	0.0116 (7)	0.0192 (8)
C11	0.0416 (8)	0.0477 (10)	0.0457 (9)	0.0108 (7)	0.0081 (7)	0.0197 (8)
C12	0.0453 (9)	0.0457 (10)	0.0419 (9)	0.0117 (7)	0.0044 (7)	0.0128 (8)
C13	0.0478 (10)	0.0906 (16)	0.0518 (11)	0.0219 (10)	0.0054 (8)	0.0141 (11)
C14	0.0620 (12)	0.138 (2)	0.0514 (12)	0.0239 (13)	0.0164 (10)	0.0196 (14)
C15	0.0725 (13)	0.113 (2)	0.0420 (11)	0.0223 (12)	0.0025 (10)	0.0188 (12)
C16	0.0545 (10)	0.0749 (15)	0.0532 (11)	0.0158 (9)	−0.0066 (9)	0.0134 (10)
C17	0.0432 (9)	0.0663 (13)	0.0519 (11)	0.0134 (8)	0.0044 (8)	0.0185 (9)
C18	0.0621 (11)	0.0881 (17)	0.0470 (11)	0.0220 (10)	0.0057 (9)	0.0169 (11)
C19	0.0634 (12)	0.120 (2)	0.0508 (12)	0.0199 (13)	−0.0005 (9)	0.0295 (13)
C20	0.0599 (12)	0.116 (2)	0.0783 (16)	0.0254 (13)	0.0060 (11)	0.0555 (16)
C21	0.0739 (13)	0.0754 (16)	0.0897 (16)	0.0222 (11)	0.0032 (12)	0.0422 (14)
C22	0.0677 (12)	0.0597 (14)	0.0642 (12)	0.0129 (9)	−0.0033 (9)	0.0257 (11)
C23	0.0463 (9)	0.0648 (13)	0.0449 (10)	0.0096 (8)	0.0081 (7)	0.0240 (9)
C24	0.0504 (9)	0.0522 (11)	0.0458 (10)	0.0135 (8)	0.0078 (7)	0.0133 (8)
C25	0.0403 (8)	0.0432 (10)	0.0439 (9)	0.0064 (7)	0.0046 (7)	0.0137 (8)
C26	0.0530 (9)	0.0535 (12)	0.0508 (10)	0.0179 (8)	0.0109 (8)	0.0163 (9)
C27	0.0445 (8)	0.0455 (10)	0.0431 (9)	0.0114 (7)	0.0069 (7)	0.0103 (8)
C28	0.0397 (8)	0.0527 (11)	0.0461 (10)	0.0114 (7)	0.0022 (7)	0.0120 (8)
C29	0.0404 (8)	0.0587 (12)	0.0454 (9)	0.0135 (7)	0.0081 (7)	0.0147 (9)
C30	0.0992 (15)	0.0679 (15)	0.0585 (13)	0.0323 (12)	0.0211 (11)	0.0154 (11)
C31	0.1139 (19)	0.0819 (18)	0.0553 (14)	0.0197 (14)	0.0196 (13)	0.0005 (13)
C32	0.0642 (12)	0.104 (2)	0.0472 (12)	0.0100 (12)	0.0097 (9)	0.0199 (13)
C33	0.0860 (15)	0.0902 (19)	0.0625 (14)	0.0214 (13)	0.0101 (11)	0.0380 (14)
C34	0.0845 (13)	0.0593 (14)	0.0558 (12)	0.0146 (10)	0.0066 (10)	0.0174 (10)
N1	0.0417 (7)	0.0494 (9)	0.0485 (8)	0.0147 (6)	0.0088 (6)	0.0214 (7)
N2	0.0490 (8)	0.0593 (10)	0.0444 (8)	0.0231 (7)	0.0120 (6)	0.0207 (7)
N3	0.0499 (8)	0.0735 (11)	0.0438 (8)	0.0295 (7)	0.0071 (6)	0.0216 (8)
N4	0.0417 (7)	0.0472 (9)	0.0465 (8)	0.0127 (6)	0.0045 (6)	0.0136 (7)
N5	0.0512 (8)	0.0588 (10)	0.0441 (9)	0.0247 (7)	0.0042 (7)	0.0119 (8)
N6	0.0547 (8)	0.0642 (11)	0.0449 (8)	0.0263 (7)	0.0072 (7)	0.0159 (8)
O1	0.0492 (6)	0.0641 (9)	0.0501 (7)	0.0244 (6)	0.0089 (5)	0.0218 (6)
O2	0.0679 (8)	0.0774 (10)	0.0485 (7)	0.0406 (7)	0.0013 (6)	0.0124 (7)

Geometric parameters (Å, º) top

C1—C2	1.381 (2)	C19—C20	1.375 (3)
C1—C6	1.389 (3)	C19—H19	0.9300
C1—H1	0.9300	C20—C21	1.361 (3)
C2—C3	1.362 (3)	C20—H20	0.9300
C2—H2	0.9300	C21—C22	1.378 (2)
C3—C4	1.364 (3)	C21—H21	0.9300
C3—H3	0.9300	C22—C23	1.386 (3)
C4—C5	1.385 (2)	C22—H22	0.9300
C4—H4	0.9300	C23—C24	1.464 (2)
C5—C6	1.379 (3)	C24—C25	1.340 (2)
C5—H5	0.9300	C24—H24	0.9300
C6—C7	1.469 (2)	C25—C27	1.450 (2)
C7—C8	1.334 (2)	C25—C26	1.493 (2)
C7—H7	0.9300	C26—H26A	0.9600
C8—C10	1.453 (2)	C26—H26B	0.9600
C8—C9	1.487 (2)	C26—H26C	0.9600
C9—H9A	0.9600	C27—N4	1.2766 (19)
C9—H9B	0.9600	C27—H27	0.9300
C9—H9C	0.9600	C28—O2	1.2302 (18)
C10—N1	1.273 (2)	C28—N6	1.346 (2)
C10—H10	0.9300	C28—N5	1.358 (2)
C11—O1	1.2269 (17)	C29—C34	1.363 (3)
C11—N2	1.355 (2)	C29—C30	1.373 (3)
C11—N3	1.356 (2)	C29—N6	1.410 (2)
C12—C13	1.373 (2)	C30—C31	1.380 (3)
C12—C17	1.378 (2)	C30—H30	0.9300
C12—N3	1.406 (2)	C31—C32	1.354 (3)
C13—C14	1.368 (3)	C31—H31	0.9300
C13—H13	0.9300	C32—C33	1.353 (3)
C14—C15	1.374 (3)	C32—H32	0.9300
C14—H14	0.9300	C33—C34	1.382 (3)
C15—C16	1.359 (3)	C33—H33	0.9300
C15—H15	0.9300	C34—H34	0.9300
C16—C17	1.375 (3)	N1—N2	1.3691 (17)
C16—H16	0.9300	N2—H2'	0.881 (9)
C17—H17	0.9300	N3—H3'	0.868 (9)
C18—C19	1.383 (3)	N4—N5	1.3679 (18)
C18—C23	1.390 (3)	N5—H5'	0.879 (9)
C18—H18	0.9300	N6—H6'	0.872 (9)

C2—C1—C6	121.3 (2)	C21—C20—H20	120.2
C2—C1—H1	119.4	C19—C20—H20	120.2
C6—C1—H1	119.4	C20—C21—C22	120.8 (2)
C3—C2—C1	120.0 (2)	C20—C21—H21	119.6
C3—C2—H2	120.0	C22—C21—H21	119.6
C1—C2—H2	120.0	C21—C22—C23	121.1 (2)
C2—C3—C4	119.84 (18)	C21—C22—H22	119.5
C2—C3—H3	120.1	C23—C22—H22	119.5
C4—C3—H3	120.1	C22—C23—C18	117.31 (16)
C3—C4—C5	120.4 (2)	C22—C23—C24	124.73 (16)
C3—C4—H4	119.8	C18—C23—C24	117.95 (18)
C5—C4—H4	119.8	C25—C24—C23	130.34 (16)
C6—C5—C4	120.90 (19)	C25—C24—H24	114.8
C6—C5—H5	119.6	C23—C24—H24	114.8
C4—C5—H5	119.6	C24—C25—C27	116.69 (15)
C5—C6—C1	117.52 (16)	C24—C25—C26	125.97 (15)
C5—C6—C7	122.88 (17)	C27—C25—C26	117.30 (14)
C1—C6—C7	119.57 (17)	C25—C26—H26A	109.5
C8—C7—C6	127.81 (16)	C25—C26—H26B	109.5
C8—C7—H7	116.1	H26A—C26—H26B	109.5
C6—C7—H7	116.1	C25—C26—H26C	109.5
C7—C8—C10	118.17 (15)	H26A—C26—H26C	109.5
C7—C8—C9	124.61 (15)	H26B—C26—H26C	109.5
C10—C8—C9	117.15 (14)	N4—C27—C25	121.85 (15)
C8—C9—H9A	109.5	N4—C27—H27	119.1
C8—C9—H9B	109.5	C25—C27—H27	119.1
H9A—C9—H9B	109.5	O2—C28—N6	123.87 (15)
C8—C9—H9C	109.5	O2—C28—N5	120.66 (16)
H9A—C9—H9C	109.5	N6—C28—N5	115.48 (14)
H9B—C9—H9C	109.5	C34—C29—C30	118.95 (17)
N1—C10—C8	120.96 (15)	C34—C29—N6	122.71 (17)
N1—C10—H10	119.5	C30—C29—N6	118.29 (17)
C8—C10—H10	119.5	C29—C30—C31	120.2 (2)
O1—C11—N2	120.94 (15)	C29—C30—H30	119.9
O1—C11—N3	124.61 (14)	C31—C30—H30	119.9
N2—C11—N3	114.45 (13)	C32—C31—C30	120.5 (2)
C13—C12—C17	119.33 (16)	C32—C31—H31	119.8
C13—C12—N3	117.83 (13)	C30—C31—H31	119.8
C17—C12—N3	122.81 (15)	C33—C32—C31	119.5 (2)
C14—C13—C12	120.14 (16)	C33—C32—H32	120.3
C14—C13—H13	119.9	C31—C32—H32	120.3
C12—C13—H13	119.9	C32—C33—C34	120.8 (2)
C13—C14—C15	120.64 (19)	C32—C33—H33	119.6
C13—C14—H14	119.7	C34—C33—H33	119.6
C15—C14—H14	119.7	C29—C34—C33	120.1 (2)
C16—C15—C14	119.16 (18)	C29—C34—H34	120.0
C16—C15—H15	120.4	C33—C34—H34	120.0
C14—C15—H15	120.4	C10—N1—N2	116.30 (14)
C15—C16—C17	120.91 (16)	C11—N2—N1	120.63 (14)
C15—C16—H16	119.5	C11—N2—H2'	119.3 (11)
C17—C16—H16	119.5	N1—N2—H2'	120.1 (11)
C16—C17—C12	119.81 (17)	C11—N3—C12	127.30 (13)
C16—C17—H17	120.1	C11—N3—H3'	111.3 (11)
C12—C17—H17	120.1	C12—N3—H3'	120.4 (11)
C19—C18—C23	121.3 (2)	C27—N4—N5	116.14 (14)
C19—C18—H18	119.4	C28—N5—N4	120.26 (15)
C23—C18—H18	119.4	C28—N5—H5'	117.5 (12)
C20—C19—C18	119.9 (2)	N4—N5—H5'	122.2 (12)
C20—C19—H19	120.0	C28—N6—C29	125.66 (14)
C18—C19—H19	120.0	C28—N6—H6'	113.7 (15)
C21—C20—C19	119.53 (19)	C29—N6—H6'	120.3 (15)

C6—C1—C2—C3	−0.8 (3)	C22—C23—C24—C25	29.1 (3)
C1—C2—C3—C4	0.1 (3)	C18—C23—C24—C25	−152.1 (2)
C2—C3—C4—C5	0.5 (4)	C23—C24—C25—C27	178.40 (17)
C3—C4—C5—C6	−0.4 (3)	C23—C24—C25—C26	0.9 (3)
C4—C5—C6—C1	−0.2 (3)	C24—C25—C27—N4	−178.73 (16)
C4—C5—C6—C7	−177.99 (19)	C26—C25—C27—N4	−1.0 (2)
C2—C1—C6—C5	0.8 (3)	C34—C29—C30—C31	−0.8 (3)
C2—C1—C6—C7	178.68 (18)	N6—C29—C30—C31	176.69 (19)
C5—C6—C7—C8	−47.8 (3)	C29—C30—C31—C32	0.9 (4)
C1—C6—C7—C8	134.4 (2)	C30—C31—C32—C33	−0.1 (4)
C6—C7—C8—C10	−179.13 (17)	C31—C32—C33—C34	−1.0 (3)
C6—C7—C8—C9	−2.4 (3)	C30—C29—C34—C33	−0.2 (3)
C7—C8—C10—N1	171.39 (16)	N6—C29—C34—C33	−177.57 (17)
C9—C8—C10—N1	−5.6 (3)	C32—C33—C34—C29	1.1 (3)
C17—C12—C13—C14	0.6 (3)	C8—C10—N1—N2	−179.88 (14)
N3—C12—C13—C14	178.7 (2)	O1—C11—N2—N1	177.56 (15)
C12—C13—C14—C15	−0.1 (4)	N3—C11—N2—N1	−2.8 (2)
C13—C14—C15—C16	−0.4 (4)	C10—N1—N2—C11	177.09 (15)
C14—C15—C16—C17	0.6 (4)	O1—C11—N3—C12	3.3 (3)
C15—C16—C17—C12	−0.1 (3)	N2—C11—N3—C12	−176.34 (17)
C13—C12—C17—C16	−0.4 (3)	C13—C12—N3—C11	149.8 (2)
N3—C12—C17—C16	−178.43 (18)	C17—C12—N3—C11	−32.2 (3)
C23—C18—C19—C20	−0.4 (3)	C25—C27—N4—N5	178.64 (15)
C18—C19—C20—C21	1.2 (4)	O2—C28—N5—N4	−179.26 (16)
C19—C20—C21—C22	−0.7 (4)	N6—C28—N5—N4	0.2 (2)
C20—C21—C22—C23	−0.7 (3)	C27—N4—N5—C28	−176.31 (16)
C21—C22—C23—C18	1.4 (3)	O2—C28—N6—C29	0.5 (3)
C21—C22—C23—C24	−179.73 (19)	N5—C28—N6—C29	−179.02 (16)
C19—C18—C23—C22	−0.9 (3)	C34—C29—N6—C28	−37.1 (3)
C19—C18—C23—C24	−179.82 (19)	C30—C29—N6—C28	145.5 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5′···O1	0.88 (1)	1.99 (1)	2.8639 (19)	174 (2)
N2—H2′···O2	0.88 (1)	1.93 (1)	2.808 (2)	176 (2)
N3—H3′···N1	0.87 (1)	2.13 (2)	2.6146 (18)	115 (1)
N6—H6′···N4	0.87 (1)	2.17 (2)	2.6261 (19)	112 (2)
C13—H13···O2ⁱ	0.93	2.64	3.476 (2)	149
C32—H32···Cg1ⁱⁱ	0.93	2.79	3.518 (2)	136

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z+2.

Acknowledgements

The authors are thankful to the SAIF, STIC, Cochin University of Science and Technology, Kochi, Kerala, India for providing the instrumental facilities for single-crystal X-ray diffraction, elemental analysis, FT–IR, NMR and UV–Vis spectroscopic studies and to the SAIF IIT Madras, Chennai, India for the FT–Raman spectroscopic data. They are grateful to Dr. M. R. Prathapachandra Kurup, Department of Applied Chemistry, Cochin University of Science & Technology, Kochi-22, India, for the use of the DIAMOND software.

Funding information

Funding for this research was provided by: University of Kerala, Thiruvananthapuram, India.

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